CN104445218A - Fluoroalkylsilane modified silicon dioxide nano material as well as preparation method and application thereof - Google Patents
Fluoroalkylsilane modified silicon dioxide nano material as well as preparation method and application thereof Download PDFInfo
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- CN104445218A CN104445218A CN201410669681.0A CN201410669681A CN104445218A CN 104445218 A CN104445218 A CN 104445218A CN 201410669681 A CN201410669681 A CN 201410669681A CN 104445218 A CN104445218 A CN 104445218A
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Abstract
The invention discloses a fluoroalkylsilane modified silicon dioxide nano material. The fluoroalkylsilane modified silicon dioxide nano material is prepared by grafting fluorine-modified alkylsilane onto the surface of silicon dioxide particles, reaction raw materials of the fluoroalkylsilane modified silicon dioxide nano material are nanoscale silicon dioxide and fluorine-modified alkylsilane, and the mass ratio of the nanoscale silicon dioxide to the fluorine-modified alkysilane is (3-7):1. The invention also discloses a preparation method and an application of the fluoroalkylsilane modified silicon dioxide nano material. The fluoroalkylsilane modified silicon dioxide nano material has excellent properties such as solvent resistance, chemical stability, lower surface energy and the like, has good cohesive force on the surface of a basal material and has properties such as water draining, oil draining, fingerprint prevention, self cleaning and the like when used as a coating. The fluoroalkylsilane modified silicon dioxide nano material is simple in production process, convenient to use, safe, environment-friendly and applicable to massive popularization and application.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of silicon fluoride improved silica nano material and its preparation method and application.
Background technology
Organosilicon material has the high-low temperature resistant of low surface energy and excellence, the performance such as ageing-resistant, hydrophobic, is widely used in the fields such as the waterproofing protection of material of construction, the waterproof of fabric and soil-repellent finishing.But its essence of organosilicon material is oil loving, easily adsorbs oily dirt, thus affects the degree of cleaning of material surface.For this reason, prior art, by carrying out surface modification to organosilicon material, makes it while not changing organosilicon material proper property, reduces further the surface energy of material, strengthens its oleophobic, solvent resistant, the performance such as antifouling.But along with the raising of people's living standard, multifunctional material is more and more subject to people's attention, also more and more higher to the performance requriements of product, to adapt to higher more complicated application demand.At present, prior art modified organic silicon material cost is higher, complex process, and applicable type of substrate is limited.Therefore, how to carry out modification to material and make it possess multifunctionality, and provide the environment for use of simple production technique and safety, be direction and the problem that material supplier author is devoted to research always.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of silicon fluoride improved silica nano material with good hydro-oleophobicity is provided, to adapt to complicated and multi-functional application demand.Another object of the present invention is to the preparation method and application that above-mentioned silicon fluoride improved silica nano material is provided.
Object of the present invention is achieved by the following technical programs:
A kind of silicon fluoride improved silica nano material provided by the invention, by being prepared from silica particle surface grafting fluorine richness alkyl silane, its reaction raw materials is as follows:
Nanometer grade silica;
Fluorine richness alkyl silane: formula R
f-CH
2-CH
2-Si (OR
1)
3, wherein, R
1for methyl or ethyl, R
ffor C
nf
2n+1, 1≤n≤12, n is integer; Or the mixture of its different structure long-chain silicon fluoride;
Described reaction raw materials nanometer grade silica in mass ratio: fluorine richness alkyl silane=3 ~ 7: 1;
Described preparation process is: added in solvent and water by described nanometer grade silica, and the pH value of regulator solution system is in alkalescence; Then in solution system, add fluorine richness alkyl silane obtain silicon fluoride improved silica nano material to carry out surface graft modification to silicon dioxide granule.
Nano material of the present invention is the colourless or light blue clear solution with good stability, and its activeconstituents is nano level silicon fluoride improved silica particle.
Further, the median size of nanometer grade silica of the present invention is 10 ~ 100nm.
Another object of the present invention is achieved by the following technical programs:
The preparation method of above-mentioned silicon fluoride improved silica nano material provided by the invention, comprises the following steps:
(1) nanometer grade silica is added in solvent and water, be uniformly mixed at 35 ~ 65 DEG C of temperature, obtain solution system;
(2) keeping described temperature and add basic catalyst regulator solution system pH is 7.5 ~ 12, continues stirring 1 ~ 3h;
(3) in solution system, add fluorine richness alkyl silane, at 35 ~ 65 DEG C of temperature, continue stirring reaction 2 ~ 6h, obtain clear solution; Adding neutralization reagent regulator solution pH value is 5 ~ 7, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Further, preparation method of the present invention described solvent in mass ratio: water: fluorine richness alkyl silane=1 ~ 50: 1 ~ 2: 1 ~ 2.Described solvent is one in ethanol, ethylene glycol, Virahol, Isopropanediol or its combination.Described basic catalyst is sodium hydroxide, strong aqua, sodium ethylate.Described neutralization reagent is ammonium chloride, hydrochloric acid, acetic acid.
Above-mentioned silicon fluoride improved silica applications to nanostructures provided by the invention, is applicable to the surface treatment of glass, pottery, metal, plastics, rubber, electronic devices and components.
The present invention has following beneficial effect:
(1) silicon fluoride improved silica nano material of the present invention, stable performance, stability in storage is good, at room temperature place 6 months not stratified, without obvious sediment, have high-low temperature resistant, the ageing-resistant performance of the excellence that inorganic materials and organosilicon material have, also impart the excellent properties such as coating solvent resistant, chemically stable, lower surface energy because of the introducing of fluoro-containing group simultaneously.
(2) nano material of the present invention and substrate surface are with chemical bonds, strong adhesion, all there is good sticking power (test according to GB/T 9286-1998 on glass, pottery, metal, plastics, rubber, electronic devices and components surface, sticking power all reaches 0 grade), coating after solidification is excellent performance in hydrophobic, oleophobic, 113 ° are greater than with the contact angle of water, be greater than 100 ° with the contact angle of oil, give substrate surface and there is waterproof, grease proofing, anti-fingerprint and self-cleaning function.
(3) coating is colourless or light blue transparent liquid, is coated on substrate surface and forms colorless and transparent film, do not affect base material outward appearance; To the light of 300 ~ 900nm without absorption, do not affect the transparency of glass, and there is good resistance to ultraviolet ageing-resistant performance, its function can be played for a long time.
(4) production technique is simple, and easy to use, volatile matter is mainly alcohols that is substantially nontoxic or low toxicity, safety and environmental protection.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment one:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 30g nano level (10 ~ 100nm) silicon-dioxide is added in 500g ethanol and 10g water, at 35 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add strong aqua regulator solution system pH is 10, continues to stir 1h;
(3) in solution system, add 10g ten trifluoro octyl group Trimethoxy silane, at 35 DEG C of temperature, continue stirring reaction 2h, obtain clear solution; Instillation ammonium chloride regulator solution pH value is 5, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Embodiment two:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 50g nano level (10 ~ 100nm) silicon-dioxide is added in 300g ethanol and 10g water, at 45 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add sodium hydrate regulator solution system pH is 11, continues to stir 1.5h;
(3) in solution system, add 10g ten trifluoro octyltri-ethoxysilane, at 45 DEG C of temperature, continue stirring reaction 3h, obtain clear solution; Instillation hydrochloric acid conditioning solution pH value is 6, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Embodiment three:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 70g nano level (10 ~ 100nm) silicon-dioxide is added in 100g Virahol and 10g water, at 55 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add sodium ethylate regulator solution system pH is 12, continues to stir 2h;
(3) in solution system, add 10g 17 fluorine decyl Trimethoxy silane, at 55 DEG C of temperature, continue stirring reaction 4h, obtain clear solution; Instillation acetic acid regulator solution pH value is 7, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Embodiment four:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 70g nano level (10 ~ 100nm) silicon-dioxide is added in 50g Isopropanediol and 10g water, at 65 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add sodium hydrate regulator solution system pH is 9, continues to stir 2.5h;
(3) in solution system, add 10g 17 fluorine decyl triethoxyl silane, at 65 DEG C of temperature, continue stirring reaction 5h, obtain clear solution; Instillation ammonium chloride regulator solution pH value is 7, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Embodiment five:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 50g nano level (10 ~ 100nm) silicon-dioxide is added in 200g ethanol and 10g water, at 35 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add sodium hydrate regulator solution system pH is 8, continues to stir 1h;
(3) in solution system, add 10g ten trifluoro octyl group Trimethoxy silane, at 35 DEG C of temperature, continue stirring reaction 3h, obtain clear solution; Instillation hydrochloric acid conditioning solution pH value is 6, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Embodiment six:
The preparation method of the present embodiment silicon fluoride improved silica nano material, its step is as follows:
(1) 30g nano level (10 ~ 100nm) silicon-dioxide is added in 100g ethanol and 10g water, at 35 DEG C of temperature, be uniformly mixed 30min, obtain solution system;
(2) keeping said temperature and add sodium ethylate regulator solution system pH is 8, continues to stir 1h;
(3) in solution system, add 10g 17 fluorine decyl Trimethoxy silane, at 35 DEG C of temperature, continue stirring reaction 4h, obtain clear solution; Instillation ammonium chloride regulator solution pH value is 6, filters reaction product and namely obtains silicon fluoride improved silica nano material.
Performance test:
The silicon fluoride improved silica nano material prepared with the above embodiment of the present invention, adopt crystal pulling method to prepare silicon fluoride improved silica film at transparent glass surface, and test sticking power, acid resistance, resistant of high or low temperature, artificial accelerated aging and the contact angle with water and glycerine.Test result is as shown in table 1.
The performance index of silicon fluoride improved silica nano material prepared by table 1 various embodiments of the present invention
A kind of silicon fluoride improved silica of the present invention nano material and its preparation method and application, its reaction raw materials composition and preparation method's processing parameter are not limited to the above-mentioned embodiment enumerated.
Claims (8)
1. a silicon fluoride improved silica nano material, is characterized in that: by being prepared from silica particle surface grafting fluorine richness alkyl silane, its reaction raw materials is as follows:
Nanometer grade silica;
Fluorine richness alkyl silane: formula R
f-CH
2-CH
2-Si (OR
1)
3, wherein, R
1for methyl or ethyl, R
ffor C
nf
2n+1, 1≤n≤12, n is integer; Or the mixture of its different structure long-chain silicon fluoride;
Described reaction raw materials nanometer grade silica in mass ratio: fluorine richness alkyl silane=3 ~ 7: 1;
Described preparation process is: added in solvent and water by described nanometer grade silica, and the pH value of regulator solution system is in alkalescence; Then in solution system, add fluorine richness alkyl silane obtain silicon fluoride improved silica nano material to carry out surface graft modification to silicon dioxide granule.
2. silicon fluoride improved silica nano material according to claim 1, is characterized in that: the median size of described nanometer grade silica is 10 ~ 100nm.
3. the preparation method of one of claim 1-2 described silicon fluoride improved silica nano material, is characterized in that comprising the following steps:
(1) nanometer grade silica is added in solvent and water, be uniformly mixed at 35 ~ 65 DEG C of temperature, obtain solution system;
(2) keeping described temperature and add basic catalyst regulator solution system pH is 7.5 ~ 12, continues stirring 1 ~ 3h;
(3) in solution system, add fluorine richness alkyl silane, at 35 ~ 65 DEG C of temperature, continue stirring reaction 2 ~ 6h, obtain clear solution; Adding neutralization reagent regulator solution pH value is 5 ~ 7, filters reaction product and namely obtains silicon fluoride improved silica nano material.
4. the preparation method of silicon fluoride improved silica nano material according to claim 3, is characterized in that: described solvent in mass ratio: water: fluorine richness alkyl silane=1 ~ 50: 1 ~ 2: 1 ~ 2.
5. the preparation method of the silicon fluoride improved silica nano material according to claim 3 or 4, is characterized in that: described solvent is one in ethanol, ethylene glycol, Virahol, Isopropanediol or its combination.
6. the preparation method of silicon fluoride improved silica nano material according to claim 3, is characterized in that: described basic catalyst is sodium hydroxide, strong aqua, sodium ethylate.
7. the preparation method of silicon fluoride improved silica nano material according to claim 3, is characterized in that: described neutralization reagent is ammonium chloride, hydrochloric acid, acetic acid.
8. one of claim 1-2 described silicon fluoride improved silica applications to nanostructures, is characterized in that: described nano material is used for the surface treatment of glass, pottery, metal, plastics, rubber, electronic devices and components.
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| CN106477590A (en) * | 2016-10-26 | 2017-03-08 | 安徽理工大学 | A kind of preparation method of high solids content nano silicon stable aqueous suspension |
| CN106905807A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Transparent hydrophobic oleophobic functional paint and its transparent hydrophobic oleophobic functional coating of formation |
| CN108587186A (en) * | 2018-05-11 | 2018-09-28 | 中国科学院化学研究所 | Modified white carbon black of fluorine silicone rubber reinforcement and preparation method thereof, fluorine silicone rubber |
| CN108977919A (en) * | 2018-06-25 | 2018-12-11 | 太极石股份有限公司 | A kind of antibacterial far infrared health care rapid-curing cutback nylon fibre and its preparation method and application |
| CN109355012A (en) * | 2018-10-31 | 2019-02-19 | 西安近代化学研究所 | A kind of preparation method and application containing Nano diamond fluorine-containing organic silicon hydrophobing agent |
| CN109481989A (en) * | 2018-09-10 | 2019-03-19 | 张国隆 | A kind of high temperature resistant dehumidifying ceramic element and preparation method thereof |
| CN111097518A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Supported solid alkali and preparation method thereof |
| CN114196049A (en) * | 2021-12-13 | 2022-03-18 | 无锡创彩光学材料有限公司 | Preparation method of strong hydrophobic polyimide film |
| CN115873310A (en) * | 2022-11-29 | 2023-03-31 | 佛山市恒洁凯乐德卫浴有限公司 | Pollution-resistant integrated basin, preparation method thereof, modified silicon dioxide and sanitary ware |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905807A (en) * | 2015-12-22 | 2017-06-30 | 北京奥托米特电子有限公司 | Transparent hydrophobic oleophobic functional paint and its transparent hydrophobic oleophobic functional coating of formation |
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| CN108587186A (en) * | 2018-05-11 | 2018-09-28 | 中国科学院化学研究所 | Modified white carbon black of fluorine silicone rubber reinforcement and preparation method thereof, fluorine silicone rubber |
| CN108587186B (en) * | 2018-05-11 | 2020-09-11 | 中国科学院化学研究所 | Modified white carbon black for reinforcing fluorosilicone rubber, preparation method thereof and fluorosilicone rubber |
| CN108977919A (en) * | 2018-06-25 | 2018-12-11 | 太极石股份有限公司 | A kind of antibacterial far infrared health care rapid-curing cutback nylon fibre and its preparation method and application |
| CN109481989A (en) * | 2018-09-10 | 2019-03-19 | 张国隆 | A kind of high temperature resistant dehumidifying ceramic element and preparation method thereof |
| CN109481989B (en) * | 2018-09-10 | 2021-02-26 | 景应政 | High-temperature-resistant dehumidifying ceramic filter element and preparation method thereof |
| CN111097518A (en) * | 2018-10-29 | 2020-05-05 | 中国石油化工股份有限公司 | Supported solid alkali and preparation method thereof |
| CN109355012A (en) * | 2018-10-31 | 2019-02-19 | 西安近代化学研究所 | A kind of preparation method and application containing Nano diamond fluorine-containing organic silicon hydrophobing agent |
| CN114196049A (en) * | 2021-12-13 | 2022-03-18 | 无锡创彩光学材料有限公司 | Preparation method of strong hydrophobic polyimide film |
| CN114196049B (en) * | 2021-12-13 | 2023-11-07 | 无锡创彩光学材料有限公司 | Preparation method of strong-hydrophobicity polyimide film |
| CN115873310A (en) * | 2022-11-29 | 2023-03-31 | 佛山市恒洁凯乐德卫浴有限公司 | Pollution-resistant integrated basin, preparation method thereof, modified silicon dioxide and sanitary ware |
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Application publication date: 20150325 |